New acid wool dyestuffs of the anthraquinone series and process of making same



Patented Oct. 4, 1932 UNITED STATES PATENT oFFics I RUDOLF MIILLER'AND ERNST HON OLD, OIE 1iRA1\'|'KIOR'I.-ON-'lHE-1VIAI1\l'-FECHEN'THIEIIVI,

GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC, 01? NEW YORK, N. Y., A. 4

CORPORATION OF DELAWARE NEW ACID WOOL DYESTUFFS OF THE ANTH RAQUINONE SERIES AND PROCESS OF MAKING- SAME No Drawing. Application filed March 14, 1929, Serial No. 347,164, and in Germany March 17, 1928.

Our present invention relates to new acid wool dyestuffs of the anthraquinone series and to processes of preparing them.

lVe have found that valuable acid wool dyestuffs, useful also as parent materials for the manufacture of further dyestuffs, are obtained by causing the diaZo-compound of an 1-amino-anthraquinone-2-sulfonic acid compound corresponding to the general formula:

(i) NH2 SOQH wherein Y means halogen, to react with a compound of the general formula:

probably replaced by substituted amino-.

groups. The exchange'w hich takes place in these two positions occurs with a difl'erent facility. It varies according to the reaction conditions and to the compounds used as starting materials. Therefore it is possible to introduce a substituted amino-group at first into one of these positions, ordinarily into the l-position, and then a further substituted amino-group, which may be different from the first one, into the other position. In thelatter case dyestuffs are obtained which contain differently substituted amino-groups in their molecules. As starting material for our present process also l-diazo-t-aryl aminoanthraquinone-Q-sulfonic acid compounds may be used, in which a substituted amino group is already present in the 4r-POSltlO1'l.

As according to the above-mentioned assumption several reactions take place besides each other, the dyestuffs prepared by our process are generally mixtures of a few chemical compounds, which are diflicult to be separated in consequence of the similarity of their properties. I

Our process may be carried out by introducing the diazo-compound into an excess of the base. In order to moderate the great disengagement of heat which spontaneously occurs, an indifferent solvent, such as benzene or nitrobenzene, may advantageously be added in many cases. The process may also be effected in the presence of water e. g. by using a moist paste of the diazo-compound.

'The new dyestufis prepared by our process dye wool from an acid bath bluish to grey to' black shades of a good fastness and levelling property.

Primary aromatic bases yield especially valuable dyestufis which though being probably mixtures of several dyestuffs-exhibit a good fastness and an excellent levelling property.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees; but we wish it to be understood that our invention is not limited to the examples given, nor" to theexact conditions stated therein.

Example 1 The diazo compound, dried in the air, of

14 parts of 'l-amino-bromo-anthraquinone- 2-sulfonic acid isintroduced at O to +5 during half an hour, while well cooling, into 30 parts of aniline mixed with 0.1 parts of. copper powder. With a strong evolution of nitrogen and a great disengagement of heat the reaction mass becomes dark brown In order to finish the reaction the temperature is allowed to arise to 30 and maintained. After the addition'of formed dyestufi' is precipitated by addition of commonsalt. It is a black powder easily soluble in water, soluble in concentrated sulfuric acid to a feebly colored solution, which becomes intensely blue when mixed with para-formaldehyde. The dyeings on wool I show neutral grey to black shades of a very good fastness; V A I Ewample 2 1, 15 parts of 1-diazo-4-bromo-anthraquin- ,one 2-sulfonic acid, dried in the air, are

' gradually added while stirring and cooling by ice to a suspension of 0.1 part of copper acet'ate 111.40 parts hexahydro aniline. When the evolution of nitrogen has ceased, the reaction mass is further. stirred at 40-50"for one hour.

' 'Ewample- 3 15 parts of a water-containing paste corresponding to9 parts of dry l-diazo-d-bromoanthraquinone-2-sulfonic acid. are introduced' into a mixture of 0.1 part of copper powder and 40 parts of aniline. perature is first maintained at 20 by cooling, then increased to about 30 until the evolution of nitrogen has ceased.

The mass is worked up as described the foregoing examples. The dyestufi thus obtained corresponds as to its properties to that of Example Asimilar dyestufi is obtained by substituting the copper powder by another catalyst as, for'instance, zinc. When no'catalyst is applied to the mass, a dyestuff is formed which dissolves in concentrated sulfuric. acid with a greenish tint and dyes Wool dark blue shades. c 1

' Example 4 14 parts of the sodium salt of l-amino-4 phenyl aminoeanthraquinone-2-sulfonic acid are dissolved in water and diazotized at 10-15 by means of hydrochloric acid and 2.5 parts of sodium nitrite. 'The difiiculty sol-.J

uble diazonium compoundis filtered off." It

is introduced at room temperature, while cooling, into a mixture of parts of aniline:

and 0.1 part of copper powder. The reaction is finished by warming the mass to and the product is isolated as explained above. The dyestufli' thus formed is substantially identical to that of Example 1.

Other bases, as para-toluidine, ortho-anisidine or mono-acetyl-dlaminobenzene, used"v The tem instead of aniline yield analogous dyestuiis. Emample 5 parts of moist l-diazo-ebromo-anthraquinone-2 sulfonic acid containing 39.3 parts of the dry diazo-compound are made into a paste with 400 parts 0]": water. Then a solution of 11.2 parts of aniline in 40 parts of acetic acid of 50% strength is added. After ing the reaction mass spontaneously becomes warm. and darkens quickly. It is then shortly warmed to 70-80? in order to finish I the reaction. The excess or aniline is removed by means of steam, the remaining dye stuff solution is filtered and mixed with com mon salt. The dyestuii thus isolated is substantially identical with that "desoribed in Example 1.

When other acid-binding .means, such as caustic alkalies, bicarbonates, sodium acetate or ammonia are used, analogous products are obtained according to thej reaction conditions, showing besides other equal properties a somewhat 'more reddishor greenish shade as the dyestufi preparedaccording to Example 1. 3

By employing instead of the aniline used in the second stage according to this example, the corresponding amount of another base as,for instance, paratoluidine, a mixed dyestufi is obtained showingsimilar properties as that prepared from aniline alone.

'Emampl 6 wherein Y means halogen, to react with a compound of the general formula:

R1 HN/ wherein R means hydrogen or an alkyl group, and R an alkyl, cycloalkyl, aralkyl or an aryl group, in the presence of a metalcontaining catalyst and of an indifferent diluent.

2. The process which comprises causing the diazo compound of an l-amino-anthraquinone-2-sulfonic acid compound of the general formula:

i O O son1 II I 0 Y wherein Y means halogen, to react with a compound of the general formula:

R1 HN/ \R, wherein R means hydrogen or an alkyl group, and R an alkyl, cycloalkyl, aralkyl or an aryl group, in the presence of a metalcontaining catalyst.

3. The process which comprises causing the diazo compound of an l-amino-anthraquinone-.Z-sulfonic acid compound of the general formula:

0 NHz [I l SOaH wherein Y means halogen, to react with an excess of a compound of the general formula:

wherein .R means hydrogen or an alkyl group and R an alkyl, cycloalkyl, aralkyl or an aryl group.

5. The process which comprises causing the diazo compound of an l-amino-anthraquinone-Q-sulfonic acid of the formula:

H U SOaH to react with an excess of aniline in the presence of copper.

6. As new products, the acid wool dyestufis obtainable by causing the diazo compound on an l-amino-anthraquinone-Q-sulfonic acid compound of the general formula:

wherein Y means halogen, to react with an excess of a compound of the general formula:

wherein R means hydrogen or an alkyl group and R an alky1,cycloalkyl, aralkyl or an aryl group, in the presence of a metal-containing catalyst and of an indifferent diluent, which products are dark-colored powders, easily soluble in water, soluble in sulfuric acid to feebly colored solutions, dyeing wool from an acid bath bluish to grey to black shades of a very good fastness and levelling property. 7. As new products, the acid wool dyestuffs obtainable by causing the diazo compound of an l-amino-anthraquinone-Q-sulfonic acid compound of the general formula:

C") NHz 0 SOaH wherein Y means halogen, to react with an excess of a compound of the general formula:

wherein R means hydrogen or an alkyl group and R an alkyl, cycloalkyl, aralkyl or an aryl group, which products are dark-colored powders, easily soluble in water, soluble in sulfuric acid to feebly colored solutions, dyeing wool from an acid bath bluish to grey to black shades of a very good fastness and levelling property.

8. As a new product, the acid Wool dyestufl' obtainable by causing the diazo compound of 1-amino-t-bromo-anthraquinon-2-sulfonic acid ofthe formula:

(I) NHn .SOaH

l 0 Br to react with an excess of aniline in the presence of copper, Which product is a black owder, easily soluble in water, soluble in sul uric acid to a feebly colored solution becoming in-. tensely blue When mixed with para-formaldehyde, dyeing Wool from an acid loath neutral grey to black shades of a Very good fastness and levelling property;

In testimony whereof, We aflix our signa- I tures.

RUDOLF MULLER. ERNST HONOLD. 

